Process for the dyeing of polyamide fibers



United States Patent 3,468,620 PROCESS FOR THE DYEING OF POLYAMIDE FIBER U.S. Cl. 8-54 49 Claims ABSTRACT OF THE DISCLOSURE Polyamide fibers such as wool and nylon are dyed with a thickened acid dye composition containing the reaction product of a polyalkanolamine and a fatty acid, and a tetrahydronaphthalene sulfonic acid. Thioglycolic acid can be added to the dyeing mixture, which may also contain a steam-blowing control agent. The acid dye composition containing the dyeing composition used in the above process is also claimed herein.

This application is a continuation-in-part of copending patent application Ser. No. 515,717 filed Dec. 22, 196 5 as a continuation-in-part of our patent application Ser. No. 214,512, filed Aug. 3, 1962 (forfeited in favor of the former). (Application Ser. No. 515,717 has been forfelted in favor of the present application.)

The present invention concerns a process for the dyeing of polyamide fibers and also the dye liquors suitable for this process.

The continuous dyeing of polyamide fibers is known. This is done by impregnating the polyamide material with an aqueous solution of acid wool dyestuffs which may be thickened, at temperatures under the drawing temperature of these dyestuffs, then after possibly drying the goods, steaming to fix the dyestulf and/or passing the goods through a hot acid bath (acid shock process) and rinsing the goods so treated. As this process has disadvantages, eg it produces uneven dyeings, the addition of color carriers, to the impregnation liquors has already been suggested. The best of these have been found to be water-soluble condensation products of fatty acids having 8 to 14 carbon atoms or of mixtures of such acids with 2 equivalents of dialkanolamine. These condensation products are known as Kritchevsky bases and are described in U.S. Patent No. 2,089,212.

However, the use of these impregnation liquors has also a number of disadvantages. Above all, such impregnation liquors are not stable as after a few hours they separate irreversibly into two phases, one poor and the other rich in auxiliaries which makes level dyeing, particularly of large batches, more difficult. In addition, the ratio of each individual component to every other in the impregnation liquors must be exactly adjusted in order to obtain maximal dyeing yields. It is thus very difficult to obtain "ice uniform results by the known process. This adversely infiuences the industrial reliability of the process. In addition, if the dyestutf is to be fixed by passing the goods through a hot acid bath, an intermediate drying of the goods saturated with the impregnation liquor has been found to be necessary in order to avoid bleeding in the acid bath.

It has now surprisingly been found that polyamide fihers can be dyed by impregnating them with preferably thickened, aqueous solutions of acid wool dyestuffs at temperatures which are under the drawing temperature for these dyestuffs and the goods which have been impregnated and possibly dried can be finished by steaming and/or passing them through a hot acid bath, while avoiding all the disadvantages above mentioned, if the impregnation liquor contains, as color carrier, instead of the usual Kritchevsky bases as additives, a combination of (1) As color transfer agent, water soluble condensation product of 1 equivalent of fatty aciy having 8 to 15 carbon atoms, or mixtures of such acids, and 1 to 3, preferably 2 equivalents of diand/or trialkanolamine, or alkanol amides, and preferably di-lower alkanol amides of such acids, which are prepared as individual technical grade compounds;

(2) As anionic steam-blowing control agent.

(a) a preferably monosulfonated mono-alkyl-benzene or mono-alkyl-naphthalene wherein the alkyl moiety has from 8 to 20, and preferably from 9 to 14 carbon atoms, either in the form of the free monosulfonic acid or, preferably, of a water-soluble salt, especially an alkali metal or an ammonium salt thereof, the latter comprising in particular lower alkyl-ammonium and hydroxy-lower alkyl-ammonium salts;

(5) sulfonated fl-tetrahydronaphthalene or a mixture of sulfonated uand fl-tetrahydronaphthalenes, or such acid or acid mixture substituted by alkyl of 8 to 20, and preferably 9 to 14 carbon atoms, or the water-soluble salts thereof, preferably the salts of the same cations as under (0:) and of the monosulfonic acids;

( condensation products of formaldehyde, or glyoxal or acetaldehyde with, per mole thereof, about 1.2 to 2 moles of at least one, and preferably one or two of the following:

(i) benzene-sulfonic acid,

(ii) naphthalene-sulfonic acid,

(iii) tetrahydronaphthalene-sulfonic acid, and/or (iv) a methyl-substituted compound of (i) to (iii) inclusive, in free acid form or in the form of watersoluble salts thereof, preferably with the same cations as defined under (a); as well as (3) If desired, thioglycolic acid or its water soluble salts which have a swelling action on polyamide.

The dyebaths thus prepared which are used as pad liquors, are preferably heated to about 40 to 60 C. before introducing the goods to be dyed thereinto. The pH of the pad liquors should be in the range of from 2 to about 8 to 9. Acid pH values are attained by addition of acidic substances, preferably formic or acetic acid to the pad liquors. When dyeing at pH values above 5.5 to 6, and particularly at the neutral to alkaline pH, it is often recommended to treat the dyed fibers in a subsequent acid bath of :a pH between 2 and 4.

In this way, uniform dyeings are obtained, even with large batches. In addition, a hot acid bath can be used without an intermediate drying and without any substantial bleeding.

The drawing temperature of the dyestuffs used, i.e. the temperature at which the dyestulf draws onto the fiber in about 1 minute, is generally 60 C. or higher. Thus in the process according to the invention, impregnation must be performed below this temperature.

This process is suitable for the continuous dyeing of polyamides, in particular, of wool. Principally fi-tetrahydronaphtalene sulphonic acid or its water soluble salts are used according to the invention as component (2).

If, in order to obtain better penetration with the dyestuif used it is desired that the impregnation liquor also contain thioglycolic acid, the amount of the latter is preferably 0.1 to 3 g./liter.

The terms tetrahydronaphthalene sulfonic acid, sulfonated alkyl-benzene, snlfonated tetrahydronaphthalene and disulfonated dinaphthyl-alkene as used in this specification and the appended claims means the free acid as well as its water soluble, and particularly its alkali metal and ammonium salts, the latter comprising besides N-substituted ammonium also N-lower alkyl-substituted and N-(hydroxy-lower alkyl)-substituted ammonium salts.

While use of the control agents defined under (2) (13), supra, requires dyeing from a neutral to alkaline aqueous medium which is often undesirable, especially when dyeing wool, use of control agents as defined under (2)(m) permits dyeing also from an acid medium and pH of which is at least 2 or higher. This makes it possible to use such industrially valuable dyes as Eriochrome Black T (C. I. No. 14645) which requires after-chroming at pH value below 5.

Particularly preferred are foam-forming control agents as defined under (2) (,8), supra, which are alkyl-benzenesu'lfonic acids or alkyl-phenol-sulfonic acids the alkyl moiety of which has from 9 to 14 carbon atoms, above all, 4-(l-methyl-undecyl)-benzene-sulfonic acid, 4-(tetrapropylene)-benzene-sulfonic acid or 4-nonyl-phenol-sulfonic acid, since these agents assist in obtaining particularly stable aqueous dye preparations and dyeings of even, deep shades.

These control agents are preferably used in the form of their water-soluble salts, especially their alkali metal or ammonium salts; however, their alkylor hydroxyalkyl-ammonium salts can also be used. Examples of suitable cations in such salts are the lithium, potassium, sodium, ammonium, fi-hydroxy-ethyl-ammonium, or bis- (fl-hydroxymethyD-ammoniurn ions.

The ratio of color transfer agent to blowing control agent should be in the range of from 1:1 to about 5:1.

The fatty acid diand/or tri-alkanolamine condensation products used in the combination according to the invention can be produced according to the process described in US. Patent 2,089,212 mentioned above. Diand tri-ethanolamine condensation products are preferred. They are produced by heating the fatty acids with l-3 equivalents of diand/or tri-ethanolamine, in particular diethanolamine, while splitting off more than 1 mol of water. Marketed mixtures known as coconut fatty acids are mainly used as fatty acids. They consist mainly of lauric acid and also contain in varying amounts the fatty acids having 8, and 14 carbon atoms. The preferred diethanolamine can be wholly or partly replaced by other low alkanolamines, e.g. by triethanolamine, di-2-propanolamine or di-3-propanolamine. Particularly when using trialkanolamines and fatty acids having 8 to 12 carbon atoms, even in a molecular ratio of 1:1 with splitting off of 1 mol of water, the condensation product is sufficiently distributable in the dye liquor. Generally, however, it is advantageous if a multiple of the stoichiometric amount, preferably double the amount of alkanolamine is used. In addition, it is favourable if at least one mol of the alkanolamine used also contains hydrogen bound to the nitrogen so that acid amide formation is possible. The condensation products used according to the invention are complex mixtures of fatty acid ethanolamides and fatty acid aminoalkanol esters. The fatty acid alkanolamide condensation products moiety is about 50-80% by weight and that of the esters is about 5-15% by weight. The difference mainly consists of uncondensed alkanolamine.

It is also possible to use, instead of such fatty acid amide/ester mixtures, products which consist of up to more than of fatty acid amides which are obtained by reacting the esters of lower alkanols and higher fatty acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, decyloxyacetic acid, lauryloxyacetic acid, decylthioacetic acid or laurylthioacetic acid, and preferably coconut oil fatty acid, e.g. the methyl or ethyl ester of such acid, in the presence of sodium ethanolate or potassium ethanolate, according to the procedure described in British Patent 631,367, with an aliphatic amine, preferably with one of the following:

(a) Monohydroxy-alkylamines, e.g., ,B-hydroxy-ethylamine, y-hydroxy-propylamine, or di-hydroxy-alkylamines, e.g. ti,'y-dihydroxy-propylamine;

(b) Bis-(w-hydroxyalkyl)-amines, e.g., bis-(fi-hydroxyethyl)-amine, bis(('y-hydroxy-propyl)-amine, bis-(ormethyl-B-hydroxyethyl) -amine;

(c) N-alkyl-N-(hydroxyalkyl)-amines, e.g. N-methylor N-ethyl-N-(fi-hydroxyethyD-amine, or N-methylor N- ethyl-N-('y-hydroxypropyl)-amine.

In the definition of amines enumerated above under (a), (b) and (0), alkyl represents preferably lower alkyl i.e. alkyl of at most 4 carbon atoms.

Most preferred amides are those of amines defined under (b), wherein alkyl has from 2 to 3 carbon atoms, and fatty acids, especially the bis-(;8hydroxyethyl)-amides and bis-('whydroxypropyD-amides of coconut oil fatty acid, since they assist in obtaining particularly good color yields.

The acid wool dyestuffs usable according 'to the invention, i.e. the color moiety of which is an anion and which draw from a neutral to acid bath, can be of any class of dyestuffs desired. They can be, for example, metal-free, metallizable or metal-containing azo, anthraquinone, phthalocyanine or nitro dyestuffs, or met hine or triphenylmethane dyes. The dyes can be water-soluble basic as well as acid dyes, or water-dispersible dyes. Azo dyes can be mono-, disor poly-azo dyes including formazanes, and the complexing metal can be chromium, cobalt, nickel or copper. Metal-containing azo dyestuffs free from sulfonic acid groups are preferred, particularly those which contain two molecules of azo dyestuffs to one metal atom. Suitable metals therein are principally chromium or cobalt.

Polyarnide fibers, especially wool, can also be dyed by the process of the invention using chromium dyes, especially chromable azo dyes which latter are used together with salts of trivalent chromium or soluble chromates in acid medium. Furthermore, fiber reactive dyestuffs, especially fiber-reactive-azo, anthraquinone or phthalocyanine dyestuffs can be used.

Polyester fibers are dyed according to the invention preferably with dispersible dyes, while acrylic fibers are preferably dyed with aqueous solutions of suitable basic dyes, e.g. methine, azomethine, diphenylmethane or triphenylmethane dyes or with arylazo or anthraquinone dyes having an external onium group.

Suitable products known in textile printing are used as thickeners, in particular the water soluble salts of alginic acid, galactornannan, tragacanth, British gum or locust bean flour. However, cellulose derivatives such as methyl cellulose or carboxymethyl-cellulose can also be used.

Formation of deposits in the dye liquors must, of course, be avoided.

Material made of both synthetic and natural polyamides can be used as polyamide fibers which can be dyed according to the invention. Examples of natural polyamides are wool and silk; examples of synthetic polyamides are nylon 6 (Perlon), nylon 66 and nylon 16. Polyester fibers such as cellulose diacetate, cellulose triacetate, high-molecular esters of aromatic polycarboxylic acids and polyhydric alcohols, e.g. poly-(ethylene glycol polyterephthalate), as well as acrylic acids and methacrylic homopolymeric and copolymeric fibers can also be dyed by the process according to the invention. In the case of synthetic polyamides drying under thermo-fix conditions after the impregnation is favourable. The dyeing process according to the invention is principally used for W001. The fibrous material can be dyed according to the invention in any form, for example, in the form of loose stock, slubbings, tops, tow, worsted, yarn or fabrics. It can also be in the form of blended fibers, e.g. of polyamide and incrusted cellulose fibers, or in the form of mixed fabrics, e.g. of wool and polyester fibers mentioned above. It is thus possible to dye only one of the fiber compounds, e.g. the polyamide fibers, or both compounds simultaneously, by dyestufis suitable for such dyeing.

The polyamide material is impregnated by printing, coating or spraying, but preferably by treatment in the pad-mangle. The impregnation liquor as defined is advantageously prepared by first dissolving the dyestuif in an about 80 C. warm aqueous solution containing the fatty acid diand/or tri-alkanolamine condensation product, the tetrahydronaph-thalene sulfonic acid and, optionallly, thioglycolic acid, and advantageously also thickeners as well as, if desirable, triethanolamine, diluting this solution with cold water up to the desired concentration, care being taken that the temperature of the liquor does not rise above about 40 C. The impregnation liquor should contain about 5 to 100 g./liter of the mixtures of assistants (l) and (2), and preferably about -60 g./liter of color transfer agent (1), e.g. fatty acid polyalkanolamine condensation product, 2-20 g./liter of blowing control agent (2), e.g. fi-tetrahydronaphthalenesulfonic acid or a mixture of aand fi-tetrahydronaphthalenesulfonic acid and, if necessary, 0.1 to 3 g./liter of thioglycolic acid, the ratio of color transfer agent to blowing control agent, as indicated by the foregoing proportions, being in most cases within the range of 1.5:1 to 5:1, but preferably about 1.5 :1 to 4:1, optimal results being obtained at about 2.5:1 to 3:1. The polyamide material is impregnated advantageously under 40 C. and then wrung out. The content of impregnating liquor should be about 40 to 110%, and not more than 130% of the dry weight of the fibers. Impregnation of polyamide material is preferably carried out at about 30 to 70 C.

Application of about 0.5 to 10% of the additive mixture of (1) and (2) calculated on the dry weight of the goods to be dyed, is thus recommended.

Apart from thioglycolic acid or its water-soluble salts, the use of which agents is recommended mainly when dyeing synthetic polyamide fibers, there may also be used other agents having a swelling effect on the fibers, such as o-phenylphenol, especially when dyeing polyterephthalate type fibers.

Solvents such as ethylene glycol monomethyl ether, or monoethyl ether (Cellosolve), thiodiethylene glycol, isopropanol or butanol, and wetting agents such as succinic acid-sulfo succinate may be added to the dye liquor as conventional adjuvants, in amounts of about 3 to 20 g. and preferably of 5 to 10 g., per liter of dye liquor.

Pad liquors according to the invention are prepared conveniently from pre-mixed, concentrated dye compositions which consist essentially of:

(a) 8 to 35 and preferably 10 to 20% by weight of dyestuff, especially a dyestuif of the kind described further below,

(b) 5 to 35% by weight of a mixture of color transfer agent and blowing control agent as defined hereinbefore, the balance of the dye composition consisting of (c) water,

(d) 0 to 5% by weight, depending on the kind of dyestuif present, of an acidic agent, preferably acetic acid, formic acid, sulfuric acid or phosphoric acid, and, optionally, an aqueous thickener, preferably galactomannan or locust bean flour, and

(e) isopropanol, or butanol and/or B-alkoxyalkanol, in order to impart to the dye composition a viscosity of about 1 to 50, and preferably 10 to 40 poise, all percentages being calculated on the total weight of the composition.

Dye liquors according to the invention are prepared from such concentrated dye compositions, by adding to to 400 g. of the latter suificient water and/or aqueous thickener solution to obtain one liter of dye liquor, the degree of dilution depending on the desired color depth of the resulting dyeings.

The impregnated polyamide material is steamed by the usual methods, advantageously with neutral saturated steam. Wool and silk are steamed at about IOU- C., synthetic fibers at about 100140 C. Synthetic polyamide and polyester fibers can also be thermofixed by heating in a dry medium to to 250 C.

When padding is done with a dye-liquor having a pH above 4 or 4.5 the dyestuif is subsequently fixed on the polyamide material by treatment in a hot acid bath having a pH in the range of about 2 to 3 by known methods. Advantageously the goods are introduced into the acid bath at 80-98 C. Acids suitable for the acid bath are inorganic and organic acids as well as acid salts. Examples of inorganic acids are sulphuric acid, phosphoric acid or hydrochloric acid. Examples of organic acids are formic acid or acetic acid; suitable acid salts are, e.g., sodium or potassium hydrogen sulphate or ammonium chloride. Organic acids are preferred, in particular formic acid. In some cases it is also useful to add Water-soluble salts, preferably water-soluble calcium salts of mineral acids, in particular calcium chloride, to the acid bath.

After the dyestutf has been fixed on the polyamide material, whether by steaming or by treatment in a hot acid bath, or by thermofixation, the material is rinsed in the usual way, advantageously with an aqueous solution of formic acid or acetic acid, depending on the type of polyamide, at 40-98" C.; detergents may be added to the rinsing liquor.

Compared with previously known processes used for the same purpose, the process for the dyeing of polyamide material according to the invention is distinguished by various advantages. For example, it gives better dyestuff yields, better penetration of the polyamide material and the dyeing is more level on this material; in addition, it is possible to dye penetratingly and evenly, woollen goods obtained by mixing wool of different origin, whereby the fastness to light is increased in many cases.

Deep shades can be obtained with very short fixation times, which means that the mechanical strength of the fibers remains essentially unimpaired, contrary to what occurs in longer fixation treatment.

Also the fibers treated according to the invention have a softer feel and can be spun better; the impregnation liquors are easily prepared; especially those prepared with compositions containing components (2) as defined under (a) and (,8) have unexpected stability, and they do not substantially soil the apparatus; finally, an intermediate drying of the impregnated goods can be avoided which is a saving in time and apparatus.

One particularly outstanding advantage of the dyeings 7 produced by the process according to the invention is the essential freedom of these dyeings from the well-known sandwich effect, which is very noticeable as a grey shimmer dulling the brilliance of the shade of dyed fabrics and giving the latter a poor aspect.

The sandwich effect is particularly disturbing in black, blue, green and red shades, while it is less readily detected in yellow and orange shades, unless the fabric is viewed at a relatively fiat angle.

In the alkylated anion-active agents listed under (2) above, the lower limit of 8 carbon atoms in the alkyl moiety is critical. For instance, dyeings produced with compositions containing alkyl-benzene-sulfonic acid or dialkyl-benzene-sulfonic acids in which each alkyl substituent has below 8, e.g., or even fewer, carbon atoms as anionic component, show a very pronounced sandwich effect.

Pad liquors according to the invention containing in the composition as component (2) substances as defined under (a) and ([3) are homogeneous and particularly stable e.g. against electrolytes, and can be preserved for several days without undue coacervation and formation or irreversible dye deposits in the vessels used for storing the dye liquors, in the case of using control agent (2) (on), even at pH values in the range below 7, and down to 2.

The dyestuif in these liquors is usually very finely distributed and in a uniform state of dispersion, which facts lead to the above mentioned uniformity and good penetration in the resulting dyeings. Dyestutf mixtures can be used without difficulty.

Moreover, dye liquors according to the invention have the desirable advantage of greatly reduced foam formation during padding while pad liquors containing only component (I), but not component (2) are liable to foam excessively in the pad mangle. Especially, as a consequence of reducing foaming, the blowing eifect on the padded fibers caused by the subsequent steam treatment, which effect increases the volume especially of padded slubbings or tow of wool and the like fibers, and thus contributes to a thorough and even distribution of the dye on all of the fibers, can be controlled to avoid excessive as well as insuflicient blowing. This is particularly important when steaming is carried out on apparatus which comprises a first pre-steaming zone from which the pre-steamed material is moved downwardly through a narrow, vertically disposed duct or channel into a second steaming zone in which it may arrive in folded condition. The pre-steamed material should pass through the vertical duct portion and optionally be laid into folds therein preferably without coming into contact with any mechanical obstructions that could, among other difficulties, cause breaking of the slubbing or the like foldable material. Excessive voluminosity of the pre-steamed material brought about in the pre-steaming zone may, of course, impede the passage of the material through the above-mentioned duct.

Dyed material obtained according to the process of the invention shows a satisfactorily reduced blowing in the presteaming zone so that it passes readily through the vertical duct of such steaming apparatus. This is particularly surprising in the case of using components as defined under (2) (a), supra, because such components themselves are well known as foaming agents; nevertheless the combination of these substances with the substances defined under (1), being themselves foam-forming and of excessive blowing eifect, afiords compositions which lead to a most desirable strong, but very brief blowing of the fiber material in the pre-heating zone itself leading to a voluminousness which recedes immediately so that the material can pass unimpeded through the abovementioned vertical duct into the second steaming zone.

It is noteworthy that each of the two components of the compositions according to the invention When used alone in the pad-dyeing process under the conditions described above causes strong sandwich effects in the dyeings produced as polyamide fibers.

Dyeings produced according to the process of the invention using a pad liquor of low pH and as component (2) some of the substance as defined under (2) show, when dyed in pastel shades, a tendency to yellow when exposed to sunlight. This is not the case when using condensation products of formaldehyde with naphthalenesulfonic acid and/ or tetrahydro-naphthalene-sulfonic acid, or such condensation products also containing methylsubstituted toluene-benezene-sulfonic acid condensed therewith.

The following non-limitative examples serve to illustrate the invention further. Temperatures are given therein in degrees centigrade. Where not otherwise expressly stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams to milliliters. C.I. means Color Index.

Example 1 40 parts of the chromium-containing monoazo dyedyestuif: 2-hydroxy 5 sulphomethylamide 1 aminobenzene +1 carboethoxyamino 7 hydroxynaphthalene (dyestuffzchromium=2: 1) are dissolved in an warm mixture consisting of 300 parts of a 2.5% aqueous so dium alginate solution, 30 parts of condensation product of coconut fatty acid and 2 equivalents of diethanolamine (according to Example 3 of US. Patent No. 2,089,212) and the solution of 15 parts of the sodium salt of S-tetrahydronaphthalene sulphonic acid in 250 parts of water. The solution obtained is diluted with about 400 parts of cold water. The temperature of this impregnating liquor should be about 40.

Wool flannel is impregnated with this liquor at 40, the goods are wrung out to a liquid content of 80% of the dry weight and then steamed at 102 with saturated steam with a slight excess pressure for 4 minutes. The steamed fabric is then treated in a 98 warm aqueous bath which contains 8 cc./litre of formic acid and then rinsed, first with hot and then with cold water.

A very level grey wool dyeing which has penetrated very well is obtained. It has no so-called sandwich effect.

If the steaming time in the above example is increased to 8, 15, 30 or 60 minutes, then dyeings of more and more colour strength but otherwise of the same value are obtained.

If, in the above example, instead of the sodium salt of fl-tetrahydronaphthalene monosulphonic acid, a corresponding amount of the sodium salt of a mixture consisting of aand ,B-tetrahydronaphthalene monosulphonic acid, or of naphthalene monosulphonic acid or of o-Xylene monosulphonic acid is used and otherwise the same procedure is followed, then grey dyeings of similar quality are obtained.

If, in the above example, instead of the dyestutf mentioned, other heavy metal-containing monoazo dyestuffs are used, e.g. those of the commercial names Irgalan Olive BGL, Irgalan Brown 7RL, Irgalan Brown 2 GL or Igralan Yellow 2 RL of I. R. Geigy A.G. Basle, Switzerland and the procedure described above is followed, then wool flannel dyed olive, brown or yellow is obtained. The dyeings have the same good penetration and evenness as that described above.

If instead of 30 parts of the condensation product of coconut fatty acids and 2 equivalents of diethanolamine, 30 parts of the condensation product of coconut fatty acid and 2 equivalents of trieth-anolarnine are used and otherwise the procedure given in the example is followed, then equally good and well penetrated dyeings are obtained.

Example 2 W001 flannel is impregnated at 40 with an impregnation liquor produced according to Example 1, first paragraph, and then wrung out to a liquor content of 80% calculated on the dry weight. The fabric which has been treated in the padding machine is passed through a 98 warm aqueous bath which contains 8 cc. per litre of 85% formic acid at such a rate that the material remains in the bath minutes. There is only inconsiderable bleeding of the dyestuif into the acid bath. The wool flannel so dyed is then washed for 5 minutes with a 45 warm aqueous solution of 0.5 g./litre nonylphenol polyglycol ether, and then rinsed with cold water. The grey dyeing obtained is well dyed through and has no so-called sandwich effect.

Example 3 W001 flannel is treated in the padding machine at 40 with an impregnation liquor which contains the dyestulf Polar Brilliant Blue GAW (CI. 61135 Acid Blue 127) instead of the metal-containing azo dyestutf mentioned in the first paragraph of Example 1, which liquor is otherwise prepared as described in Example 1, paragraph 1. The material is wrung out to a liquid content of 80% of the dry weight and then steamed for 4 minutes at 102 under slight excess pressure. The goods are then rinsedfirst with hot and then with cold water.

A very level and well penetrated blue wool dyeing is obtained which has no so-called sandwich elfect.

If instead of Polar Brilliant Blue GAW, the dyestufi of the formula CIH;

l 1 1E: NH:

is used and otherwise the same procedure as described in the example is followed, then equally good and level well penetrated material dyed red is obtained.

Example 4 Wool flannel is impregnated at 40 with an impregnating liquor produced according to Example 3 paragraph 1 and then wrung out to a liquor content of 80% of the weight of the fibres. The padded fabric is then passed through a 98 warm aqueous bath containing 8 cc./litre of 85% formic acid and 2 grams per litre of calcium chloride at such a rate that the material is in the bath for 5 minutes, during which process only inconsiderable bleeding of the dyestutf into the acid bath occurs. The goods are then washed with a 45 warm aqueous solution of 0.5 g./ litre phenol polyglycol ether and then rinsed with cold water.

The wool flannel so obtained is well penetrated and the dyeing is very level without any so-called sandwich elfect.

Example 5 40 parts of the cobalt-containing monoazo dyestuff: Z-hydroxy-l-aminobenzene-5-sulphonic acid methylamicle 1-phenyl-3-methylpyrazolone (dyestulf :coba1t=2: 1) are dissolved in an 80" warm mixture consisting of 300 parts of a 2.5% aqueous sodium alginate solution, parts of the condensation product of coconut fatty acid and 2 equivalent of diethanolamine (according to Example 3 of US. Patent No. 2,089,212) and the solution of 15 parts of the sodium salt of fi-tetrahydronaphthalene sulphonic acid in 250 parts of water. This solution is diluted with about 400 parts of cold water. The temperature of this impregnation liquor should be about Silk serge is impregnated at 40 with this liquor, the goods are wrung out to a liquid content of 80% of the dry weight and steamed with saturated steam for 4 minutes at 102 under slight excess pressure. The fabric is then rinsed first with hot and then with cold water.

A very level and Well penetrated yellow silk dyeing is obtained which has no so-called sandwich effect.

On increasing the steaming time in the above example to 8, 15, 30 or 60 minutes yellow silk dyeings of greater and greater colour strength but otherwise having the same properties are obtained.

If in the above example, instead of the dyestuff mentioned, the dyestuff Neolan Yellow 8 GE (Cl. Acid Yellow 101) is used, then yellow silk serge dyeings are obtained of equal penetration and evenness.

If instead of 30 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine, 30 parts of the condensation product of coconut fatty acid and 3 equivalents of diethanolamine are used and otherwise the procedure given in the example is followed, then equally good and well penetrated dyeings are obtained.

Example 6 Silk serge is impregnated at 40 with an impregnation liquor produced according to Example 5, paragraph 1, the goods are wrung out to a liquor content of and passed through a 98 warm aqueous bath which contains 8 cc./litre of formic acid at such a rate that the material of the dyestulf into the acid bath occurs. The dyed silk serge is then washed with a 45 warm aqueous solution of 0.5 g./litre nonylphenol polyglycol ether and afterwards rinsed with cold water.

In this way, well penetrated yellow silk serge of good evenness is obtained and there is no so-called sandwich effect.

Corresponding dyeings on silk serge of equally good penetration of the material and evenness of the dyeings are obtained if, instead of the dyestuff mentioned in the above example, Neolan Yellow 8 GE (C.I. Acid Yellow 101) is used and otherwise the procedure given above is followed.

Example 7 37.5 parts of the chromium-containing monoazo dyestulf 2-carboxyl-1-aminobenzene 1-phenyl-3 -methylpyrazolone (dyestulf:chromium=2:1) and 14.0 parts of the chromium-containing monoazo dyestufi 2-hydroxy-5-sulphomethylamido-l-aminobenzene1 carboethoxyamino- 7-hydroxynaphthalene (dyestuff:chromium=2:1) are dissolved in an 80 warrn mixture of 300 parts of a 2.5% aqueous sodium alginate solution, 10 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine, 20 parts of triethanolamine, a solution of 15 parts of the sodium salt of fi-tetrahydronaphthalene sulphonic acid and 270 parts of water and the solution obtained is diluted with about 400 parts of cold water. The temperature of this impregnation liquor should be about 40 Nylon canvas is impregnated with this liquor, wrung out to a liquid content of 50%, steamed for 8 minutes at a temperature of and then rinsed first with hot and then with cold water.

A very well penetrated and very level olive dyeing is obtained which has no so-called sandwich effect.

Example 8 Nylon canvas is impregnated at 40 with an impregnation liquor produced according to Example 8, paragraph 1.

The goods are then wrung out to a liquid content of 50% and passed through a 98 warm aqueous bath which con tains 4 cc. per liter of 85% formic acid at such a rate that the material remains in this bath for 4 minutes. Only an inconsidera-ble bleeding of the dyestufi into the acid bath occurs. The nylon canvas so dyed is then rinsed first with warm and then with cold water.

The nylon canvas so obtained is well penetrated and evenly dyed olive green.

Example 9 Canvas made of poly-e-aminocaprolactam (Perlon) is impregnated at 40 with an impregnation liquor produced according to Example 7. The goods are the wrung out to a liquor content of 50% and dried under thermo-fix conditions for 45 seconds at 190.

The Perlon canvas so impregnated is then passed through a 98 warm aqueous bath which contains 4 cc./litre of 85 formic acid and is treated for 4 minutes at the boil in this bath. It is then rinsed with warm and then cold water.

The Perlon canvas so treated is well penetrated and a level olive dyeing is obtained.

Example 10 2.5 parts of the chromium-containing monoazo dyestuif 2-carboxyl-1-amin0benzenel phenyl 3 methylpyrazolone (dyestutf:chromium=2:1) and 0.5 part of the chromium-containing monoazo dyestulf:chromium=2:l) and 0.5 part of the chromium-containing monoazo dyestuif: 2-hydroxy-5-nitro-l-aminobenzene-e l-phenyl 3 methylpyrazolone (dyestutfzchromium 2:1) are dissolved in an 80 warm mixture of 300 parts of a 2.5% aqueous sodium alginate solution, 20 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine (according to Example 3 in U.S. Patent No. 2,089,- 212), 10 parts of urea, 5 parts of the sodium salt of sulphosuccinic acid dioctyl ester, 20 parts of the sodium salt of B-tetrahydronaphthalene monosulphonic acid and 250 parts of water. The solution obtained is diluted with water up to 1000 parts by volume. Woollen worsted yarn is impregnated at 40 with this liquor, wrung out to a liquid content of 103% of the dry weight and then steamed for 8 /2 minutes at 104 with saturated steam under slight excess pressure. The goods are then washed with a solution containing 1 g./litre of nonylphenol polyglycol ether and 1 cc./litre of concentrated ammonia solution, then rinsed with water, then washed with an aqueous solution containing 2 cc./litre of 85 formic acid and, if desired, again rinsed with water.

The orange-red worsted yarn so dyed is well penetrated and the dyeing is very level. The feel of the goods is very pleasant and voluminous and they can be well combed and spun. Also after the impregnation of liquor has been left standing for weeks, level and penetrated worsted yarn is obtained.

Example 11 40 parts of chromium-containing monoazo dyestuff: 2 -hydroxy-S-sulphomethylamido 1 aminobenzene 1- carboethoxy amino 7 hydroxynaphthalene (dyestuif: chromium=2:1) are stirred in a solution produced according to Example 1, paragraph 1, but containing 500 parts of sodium alginate solution instead of 300 parts.

Woollen Worsted yarn is printed in the manner usual for vigoureux printing with this liquor with a liquor takeup of 85 The printed goods are after-treated by steaming and rinsing as described in Example 10. Grey coloured Woollen worsted yarn is obtained which is distinguished by a full, voluminous feel. The goods can be well combed and spun.

Example 12 80 parts of Eriochrome Black A (C.I. 15710) are dissolved in a 60 warm mixture of 300 parts of a 2.5% sodium alginate solution and 30 parts of a mixture of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine (according to U.S. Patent No. 2,089,212, Example 3) and the solution of 30 parts of the sodium salt of jS-tetrahydronaphthalene sulphonic acid in 250 parts of water, and also 10 parts of potassium chloride in 100 parts of water. The solution is then made up to 1000 parts with water; the temperature should be 40.

Woollen slubbing is impregnated with this liquor at 40, wrung out to a liquor content of about and steamed with saturated steam at 98 for 1 hour. It is then rinsed with an aqueous solution of 0.5 g./litre of a condensation product according to U.S.P. 2,089,212 in a back washing machine, rinsed with about 30 warm water and then acidified in a new bath with an aqueous 30 warm solution of 0.2 cc./litre or formic acid. Finally the goods are again rinsed with 30 warm water.

Woollen slubbing dyed a level black is obtained which can be well combed and spun.

Similar level-dyed woollen slubbings of vivid brownishred shade are obtained by repeating Example 12, but using in lieu of the dyestulf employed therein, 50 parts of a dyestulf being a mixture of the orange 2:1 chromium complex of the dyestulf of the formula CHaSIO:

the red dyestuff of the formula SOaH aN S $0311 and the blue dyestufi of the formula 0 NH: H l

in a weight ratio of 25 :25 :6.

Example 13 400 parts of cold water. The temperature of the solution should be about 40.

Wool flannel is impregnated with this liquor at 40, the

l ILH NH;

goods are wrung out to a liquid content of 80% of the dry weight and then steamed at 102 with saturated steam with a slight excess pressure for 4 minutes. The fabric is then rinsed first with hot and then with cold water.

A very level grey wool dyeing which has penetrated very well is obtained. It has no so-called sandwich effect.

If the steaming time in the above example is increased to 8, 15, 30 or 60 minutes, then dyeings of more and more colour strength but otherwise of the same value are obtained.

If in the above example, instead of the 15 parts of the Sodium salt of fi-tetrahydronaphthalene sulphonic acid, the same number of parts of a mixture of sodium salt of aand fi-tetrahydronaphthalene sulphonic acid or of solution salt of o-xylene sulphonic acid or 30 parts of sodium salt of naphthalene sulphonic acid are used and otherwise the same procedure as described in the example is followed, then dyeings having similar qualities are obtained.

If in the above example instead of the dyestulf mentioned, other heavy metal-containing monoazo dyestuifs are used, e.g. those of the commercial names Irgalan Olive, BGL, Irgalan Brown 7 RL, Irgalan Brown 2 GL or Irgalan Yellow 2 RL and the procedure described above is followed, then wool flannel dyed olive, brown or yellow is obtained. The dyeings have the same good penetration and evenness as that described above.

If instead of 30 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine, 30 parts of the condensation product of coconut fatty acid and 1 equivalent of triethanolarnine are used and otherwise the procedure given in the example is followed, then equally good and Well penetrated dyeings are obtained.

Example 14 Wool flannel is impregnated at 40 with an impregnation liquor produced according to example 13, first paragraph and then wrung out to a liquor content of 50% calculated on the dry weight. The fabric which has been treated in the padding machine is passed through a 98 warm aqueous bath which contains 8 cc. per litre of 85% formic acid at such a rate that the material remains in the bath minutes. There is only an inconsiderable bleeding of the dyestuflt' into the acid bath. The wool flannel so dyed is then washed for 5 minutes with a 45 warm aqueous solution of 0.5 g./litre nonylphenol polyglycol ether, and then rinsed with cold water. The grey dyeing obtained is well dyed through and has no so-called sandwich effect.

Example 15 Wool flannel is treated in the padding machine at 40 with an impregnation liquor which contains the dyestulf Polar Brilliant Blue GAW (CI. 61135 Acid Blue 127) instead of the metal-containing azo dyestuflf mentioned in the first paragraph of Example 13, which liquor is otherwise prepared as described in Example 13, paragraph 1. The material is wrung out to a liquid content of 80% of the dry weight and then steamed for 4 minutes at 102 under slight excess pressure. The goods are then rinsed first with hot and then with cold water.

A very level and well penetrated blue wool flannel 14 dyeing is obtained which has no so-called sandwich eflect. If instead of Polar Brilliant Blue GAW, the dyestuff of the formula or Neolan Yellow 8 GE (C.I. Acid Yellow 101) is used and otherwise the same procedure as described in the example is followed, then equally good and level well penetrated material dyed red or yellow respectively is obtained.

Example 16 Wool flannel is impregnated at 40 with an impregnating liquor produced according to Example 15 paragraph 1 and then wrung out to a liquor content of of the weight of the fibres. The padded fabric is then passed through a 98 warm aqueous bath containing 8 cc./litre of formic acid at such a rate that the material is in the bath for 5 minutes, during which process only inconsiderable bleeding of the dyestuff into the acid bath occurs. The goods are then washed with a 45 warm aqueous solution of 0.5 g./litre nonyl phenol polyglycol ether and then rinsed with cold water.

The wool flannel so obtained is well penetrated and the blue dyeings are very level without any so-called sandwich effect.

Example 17 40 parts of the cobalt-containing monoazo dyestuff: 2- hydroxy-l-aminobenzene-5-sulphonic acid methylamide 1 phenyl-S-methylpyrazolone (dyestuffzcobalt=2:1) are dissolved in an 80 warm mixture consisting of 300 parts of a 2.5% aqueous sodium alginate solution, 30 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine (according to Example 3 of US. Patent No. 2,089,212) and the solution of 15 parts of the sodium salt of fl-tetrahydronaphthalene sulphonic acid and 2 parts of thioglycolic acid in 250 parts of water. This solution is diluted with about 400 parts of cold water. The temperature of the solution should be about 40".

Silk serge is impregnated at 40 with this liquor, the goods are wrung out to a liquid content of 80% of the dry weight and steamed with saturated steam for 4 minutes at 102 under slight excess pressure. The fabric is then rinsed first with hot and then with cold water.

A very level and well penetrated yellow silk dyeing is obtained which has no so-called sandwich effect.

On increasing the steaming time in the above example to 8, 15, 30 or 60 minutes, yellow silk dyeings of greater and greater colour strength but otherwise having the same properties are obtained. 1

-If in the above example, instead of the dyestuff mentioned, the dyestufl Neolan Yellow 8 GE (C.I. Acid Yellow 101) is used, then yellow silk serge dyeings are obtained of equal penetration and evenness.

If instead of 30 parts of the condensation product of coconut fatty acid and 2 equivalents of diethanolamine, 30 parts of the condensation product of coconut fatty acid and 3 equivalents of diethanolamine are used and otherwise the procedure given in the example is followed, then equally good and well penertated dyeings are obtained.

Example 18 able bleeding of the dyestufi into the acid bath occurs. The dyed silk serge is then washed with a 45 warm aqueous solution of 0.5 g./litre nonylphenol polyglycol ether and afterwards rinsed with cold water.

In this way, well penetrated yellow silk serge of good evenness is obtained and there is no so-called sandwich elfect.

Corresponding yellow dyeings on silk serge of equally good penetration of the material and evenness of the dyeings are obtained if, instead of the dyestulf mentioned in the above example, Neolan Yellow 8 GE (Cl. Acid Yellow 101) is used and otherwise the procedure given above is followed.

Example 19 In order to prepare a pad liquor (a) 40 parts of Eriochrome Black A (CI. 15710), 24 parts of which are diluting agent (coupage), are pasted with 40 parts of water of 25, then there are added to the paste with stirring 750 parts of water having a temperature of 60, 7 parts of galactomannan thickener pasted with 10 parts of ethanol; the resulting liquor is heated to the boil for 2 to 3 minutes and then left to cool to about 40;

(b) parts of 85% formic acid, parts of chromium trifiuoride and 60 parts of water of 20 are mixed and the resulting slurry is added to the foregoing liquor;

(c) parts 0 fa condensation product of coconut oil fatty acid and 2 equivalents of diethanolamine prepared according to Example 3 of US. Patent 2,089,212, and 20 parts of sodium 4-( l-methyl-undecyl)-benzene-1-sulfonate (or the product containing the latter which is commercially available under the tradename of Marlon A 375) are mixed with 50 parts of Water, and

(d) 50 parts of the mixture resulting from (c) are added to the acidified liquor obtained by step (b), supra. Water is then added to the resulting composition to adjust the total volume of the dye liquor to 1000 parts. This pad liquor is very stable and can be left standing for several days without undue conservation.

(e) Woollen slubbing is impregnated with this liquor at wrung out to a liquor content of about 80% and steamed with saturated steam at 98 for 1 hour. It is then rinsed with an aqueous solution of 0.5 g./liter of sodium dodecyl-benzenesulfonate in a back washing machine at 40, and then rinsed with about 30 warm water and left to dry.

Woollen slubbing dyed a level black free from sandwich effect is obtained which can be well combed and spun.

When steamed on a two-phase steaming machine having a first pre-steaming zone above a narrow vertical duct for the pre-steamed material and a subsequent large horizontal steaming zone into which the lower exit of the duct opens, the slubbing is blown strongly but only very briefly while in the presteaming zone above the vertical zone, but the voluminousness due to the blowing efi'ect recedes promptly so that the slubbing passes through the vertical duct unimpeded.

By using in step (c) of the above Example 19, instead of sodium dodecyl-benzenesulfonate an equivalent amount of potassium p-(1,3,3,5 tetramethyl-octyl)-benzene-sulfonate, di(fi-hydroxyethyl)-ammonium p-(l methyloctyl) -benzene-sulfonate, or 1,2 di-[4 sulfo-naphthyl- (2) ]-ethane, or a condensation product of a mixture of xylene sulfuric acid and naphthalene sulfuric acid (molar ratio 5:4) with 1.7 equivalents of formaldehyde, and otherwise following the same procedure as described in Example 19, then black dyeings of similar quality are obtained.

If instead of 30 parts of the condensation product of coconut oil fatty acid and 2 equivalents of diethanolamine, 40 or 60 parts of the condensation product of coconut oil fatty acid and 2 equivalents of triethanolamine or of 30, 40, or 60 parts of coconut oil fatty acid diethanolamide, respectively, are used in step (0), supra, and otherwise the procedure given in Example 19 is followed, then equally satisfactory dyeings are obtained.

Similar satisfactory black dyeings are obtained when repeating Example 19, but using in step (c) in lieu of the 30 parts of the condensation product used therein, 25 parts of the same condensation product, an din lieu of 20 parts of the sodium salt of methylundecylbenzene sulfonic acid used therein, 10 parts of the sodium salt of the condensation product obtained from 2 equivalents of naphthalene-sulfonic acid and 1.4 equivalents of formaldehyde or 10 parts of the sodium salt of the condensation product of:

(a) 2 equivalents of naphthalene-sulfonic acid and 1.5

parts of acetaldehyde; or (b) 1 equivalent of naphthalene-sulfonic acid, 1 equivalent of tetrahydronaphthalene-sulfonic acid, and 1.5

equivalents of paraformadehyde; or (c) 1 equivalent of naphthalene-sulfonic acid, 1 equivalent of methylnaphthalene-sulfonic acid, and 1.9 equivalents of formaldehyde.

Similar level-dyed woollen slubbings of vivid brownishred shade are obtained by repeating Example 19, but using in lieu of the dyestuff employed therein, 50 parts of a dyestuif being a mixture of:

(i) the orange 2:1 chromium complex of the dyestulf of the formula (ii) the red dyestuff of the formula soart G1 :11 (iii) and the blue dyestuff of the formula 3 NHg s 0 H CH n I a 0 EN 0H;

in a weight ratio of 25 :25 :6, omitting the chromium trifiuoride, and using 15 in lieu of 20 parts of aqueous formic acid in the preparation of the pad liquor.

Example 20 Wool flannel is impregnated at 40 with an impregnation liquor produced according to step (c) of Example 19, and then wrung out to a liquor content of calculated on the wool dry weight. The fabric which has been treated in the foulard is passed through a 98 warm aqueous bath which contains 8 ml per liter of 85% formic acid at such a rate that the material remains in the bath for '17 30 minutes. There is only a negligible amount of bleeding of the dyestuff into the acid bath. The wool flannel so dyed is then washed for minutes with a 45-warm aqueous solution of 0.5 g/liter nonylphenol polyglycol ether, and then rinsed with cold water. The grey dyeing obtained is well-penetrated and has no so-called sandwich effect.

Example 21 A pad liquor is prepared as described in Example 19, but using in lieu of the 40 parts of black dye employed therein, only 5 parts of the chromium-container monoazo dyestuff obtained by coupling diazotized Z-hydroxy- S-N-methyl-sulfamyl-l-amino-benzene with l-ethoxycarbonylamino-7-hydroxynaphthalene and chroming the resulting metallizable azo dye with chromium chloride in a molar ratio of dyestuif to metal of 2:1, and adding 25 parts of aqueous 80% acetic acid in lieu of the formic acid employed in Example 19.

20 parts of the auxiliary mixture prepared as described in Example 19(c) are added in lieu of the 25 parts used in Example 19(d).

The pad liquor thus obtained is stable for several days.

Wool flannel is impregnated with this resulting liquor at 40, the goods are wrung out to a liquid content of 100% of the dry Weight and then steamed at 102 with saturated steam with slight excess pressure for 20 minutes. The steamed fabric is then rinsed, first with hot and then with cold water.

A very level Wool dyeing of grey pastel shade which has penetrated very Well is obtained. It has no sandwich effect.

If the steaming time in the above example is increased to 30 or 60 minutes, then dyeings of greater color strength but otherwise of the same quality are obtained.

Example 22 Similar results are obtained by repeating Examples 19, 20 and 21, respectively, but using in each case in lieu of the auxiliary mixture produced as described in step (c) of Examples 19, 30, 40 or 60 parts, respectively, of an auxiliary mixture prepared from the following components:

40 parts of coconut oil fatty acid N,N-di-(B-hydroxyethyl)-amide, 10 parts of diethanolammonium p-dodecyl-benzene-sulfonate, 50 parts of Water;

35 parts of the same condensation produce as used in Example 19 (c), parts of sodium p-(l,3,3,5-tetramethyl-octyl)-benzene sulfonate, 2 parts of isopropanol;

parts of the same condensation product as used in Example 19 (c), 20 parts of coconut oil fatty acid N,N-di-(f3-hydroxyethyl) -amide, 15 parts of diethanolammonium p-(l-methyl-octyl)-benzene-sulfonate, 55 parts of water;

parts of the same condensation product as used in Example 19 (c), 25 parts of diethylammonium p-nonylphenol-sulphonate, 45 parts of water;

25 parts of coconut oil fatty acid diethanolamide,

5 parts of potassium p-(l,3,3,5-tetramethyl-octyl)-benzenesulfonate,

parts of water;

20 parts of coconut oil fatty acid N,N-di-(fi-hydroxyethyl) -amide, 20 parts of sodium dodecyl-naphthalene-sulfonate, 35 parts of water;

20 parts of lauric acid N-(B-hydroxy-propyl)-amide, 10 parts of ammonium decylnaphthol-sulfonate, 35 parts of water;

20 parts of capric acid N,N-('y-hydroxy-propyl)-amide, 15 parts of ammonium p-decylbenzene-sulfonate, 35 parts of water;

10 parts of coconut oil fatty acid N-methyl-N-p-hydroxyethyl-amide,

10 parts of sodium salt of the condensation product of 1 equivalent of naphthalene-sulfonic acid, 1 equivalent of methylnaphthalene sulfonic acid and 1.6 equivalents of formaldehyde,

2 parts of isopropanol;

40 parts of coconut oil fatty acid N,N-di-([3-hydroxyethyl) -amide,

10 parts of diethanolammonium salt of the condensation product from: 1 equivalent of benZene-sulfonic acid, 1 equivalent of naphthalene-sulfonic acid and 1.4 equivalents of formaldehyde;

35 parts of coconut oil fatty acid N,N-di-(B-hydroxyethyl) -amide,

15 parts of sodium salt of the condensation product from: 1 equivalent benzene-sulfonic acid, 1 equivalent of naphthalene-sulfonic acid and 1.4 equivalents of glyoxal;

20 parts of coconut oil fatty acid N,N-di-(,6-hydroxyethyl) amide,

20 parts of diethanolammonium salt of the condensation product from: 1 equivalent of toluene-sulfonic acid, 1 equivalent of naphthalene-sulfonic acid and 1.4 equivalents of formaldehyde;

25 parts of coconut oil fatty acid N,N-di-(/8-hydroxyethyl)-amide,

25 parts of the sodium salt of the condensation product from: 1 equivalent of benzene-sulfonic acid, 1 equivalent of tetrahydronaphthalene-sulfonic acid and 1.6 equivalents of formaldehyde;

25 parts of coconut oil acid N,N-di-(B-hydroxyethyl)- amide,

5 parts of potassium salt of the condensation product from: 2 equivalents of tetrahydronaphthalene-sulfonic acid and 1.5 equivalents of formaldehyde;

20 parts of coconut oil fatty acid N,N-di-(;3-hydroxyethyl) -amide,

20 parts of the sodium salt of the condensation product from: 1 equivalent of xylene-sulfonic acid, 1 equivalent of tetrahydronaphthalene-sulfonic acid and 1.7 equivalents of formaldehyde;

20 parts of lauric acid N,-N-di-(/i-hydroxy-propyl)-amide,

10 parts of the ammonium salt of the condensation product from: 1 equivalent of toluene-sulfonic acid, 1 equivalent of tetrahydronaphthalene-sulfonic acid and 1.6 equivalents of formaldehyde;

20 parts of capric acid N,N-di-('y-hydroxy-propyl)-amide,

15 parts of the ammonium salt of the condensation product from: 1 equivalent of xylene-sulfonic acid, 1 equivalent of naphthalene-sulfonic acid and 1.5 equivalents of formaldehyde;

20 parts of coconut oil fatty acid N,N-di-( 8-hydroxyethyl)-amide,

20 parts of the sodium salt of the condensation product from: 2 equivalents of naphthalene-sulfonic acid and 1.7 equivalents of glyoxal.

Example 23 Wool flannel is treated in the foulard at 40 with an impregnation liquor which contains 20 parts of the dyestuff Polar Brilliant Blue GAW (C.I. 61135, Acid Blue 127) instead of Erichrome Black A and is otherwise prepared as described in Example 19 (a) to (d). The material is wrung out to a liquid content of 80% of the dry weight and then steamed for 15 minutes at 102 under slight excess pressure. The goods are then rinsed first with hot and then with cold water.

A very level and well penetrated blue wool dyeing is obtained which is free from sandwich effect.

If instead of Polar Brilliant Blue GAW, the dyestuff of the formula is used and otherwise the same procedure as described in the example is followed, then equally level and well penetrated material of red shade is obtained.

Example 24 40 parts of the chromium-containing monoazo dyestufi: 2-hydroxy-5-methylsulfonyl-1-aminobenzene- 1-phenyl-3 methyl-S-pyrazolone (dyestutf:chromium=2:1) are dissolved in a 60 warm mixture containing of 300 parts a 2.5% aqueous locust bean flour solution and a solution of 30 parts of a mixture consisting of coconut oil fatty acid diethanol-amide and sodium 4-(1-methyl-undecyD-benzene-sulfonate (weight ratio 1:1) in 250 parts of water. The solution obtained is diluted with 50 warm water to 900 parts by volume and the pH of the solution is adjusted to 2.5. The temperature of the solution should be about 50". Finally, water is added to make the the volume of the liquor up to one liter.

Wool flannel is impregnated with this liquor at 50, the goods are wrung out to a liquid content of about 100% of the dry weight and then steamed at 98 with saturated steam for 15 minutes. The wool flannel so dyed is then first washed for 5 minutes with a 45 warm aqueous solution of 0.5 g./liter nonylphenol polyglycol either, and then with an aqueous solution containing 2 parts by volume of 85 %-formic acid per liter, whereupon it is rinsed with cold water. The orange dyeing obtained is well penetrated and level and has no sandwich effect.

A similar satisfactory result is obtained when repeating the above example but using in lieu of the sodium methylundecylbenzene-sulfonate an equal amount of the sodium salt of the condensation product from 2 equivalents of naphthalene-sulfonic acid and 1.4 equivalents of formaldehyde.

By repeating Example 24, but using 40 parts of a 2:1 dyestuif chromium complex of one of the dyestuffs listed below, in lieu of the dyestuff used therein, then dyeings on wool flannel of similar good quality and the shade given in the right-hand column below are obtained.

acid S 0311 coupling Similar level-dyed wool flannel of vivid shades are obtained by repeating Example 24, but using in lieu of the 30 parts of dyeing assistant employed therein, 30 parts of a mixture prepared from:

(i) 50 parts of coconut oil fatty acid diethanolamide and (ii) 50 parts of ammonium p-nonylphenol-sulfonate, or in lieu of the latter component, (ii), equivalent amounts of di-ethanol-ammonium or triethanol-ammonium 4-(1- methyl-undecyl) -benzenesulfonate, or of the ammonium salt of the condensation product from 2 equivalents of xylene-sulfonic acid (commercial product) and 1.2 equivalents of formaldehyde,

or of the diethanol-ammonium salt or the triethanol-ammonium salt of the condensation product from 2 equivalents of naphthalene-sulfonic acid and 1.4 equivalents of formaldehyde.

Example 25 4 parts of the cobalt-containing monoazo dyestuflF: 2- hydroxy-l-aminobenzene-S-sulphonic acid methylamide 1-phenyl-3-methylpyrazolone (dyestufi:cobalt=2:1) are dissolved in an -warm mixture consisting of 300 parts of water, 7 parts of galactomannan thickener, 15 parts of coconut oil fatty acid diethanolamide and the 21 solution of parts of sodium 4-(l-methyl-undecyl) -benzene-Lsulfonate in 250 parts of water. The resulting solution is diluted with about 400 parts of cold water, and parts of 85%-formic acid are added thereto. The temperature of the solution should be about 40.

Silk serge is impregnated at 40 with this liquor, the goods are wrung out to a liquid content of 80% of their dry weight and steamed with saturated steam for 4 minutes at 102 under slight excess pressure. The fabric is then rinsed first with hot and then with cold water.

A very level and well penetrated yellow silk dyeing is obtained which is free from sandwich effect.

On increasing the steaming time in the above example to or 60 minutes, yellow silk dyeings are obtained which are of greater color strength but otherwise have the same good properties.

If in the above example, instead of the dyestui'f mentioned, the dyestuff of the formula is used, then yellow silk serge dyeings are obtained which are of equal good penetration and evenness.

If instead of coconut oil fatty acid diethanolamide, 30 parts of the condensation product of coconut fatty acid and 3 equivalents of diethanolamine are used and otherwise the procedure given in the example is followed, then equally good and well penetrated dyeings are obtained.

Example 26 Silk serge is impregnated at with an impregnation liquor produced according to Example 5 but using composition (d) of Example 24 as auxiliary, the goods are wrung out to a liquid content of 80%, and passed through a 98 warm aqueous bath which contains 8 ml./liter of 85% formic acid at such a rate that the material is in the bath for 5 minutes, during which process only inconsiderable bleeding of the dyestuff into the acid bath occurs. The dyed silk serge is then washed with a warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and afterwards rinsed with cold water.

In this way, well penetrated orange-yellow silk serge of good evenness is obtained and there is no so-called sandwich effect.

Corresponding dyeings on silk serge of equally good penetration of the material and evenness of the dyeings are obtained if, instead of the dyestufi mentioned in the above example, Neolan Yellow 8 GE (C.I. Acid Yellow 101) is used and otherwise the procedure given above is followed.

Example 27 37.5 parts of the chromium-containing monoazo dyestuif 2 carboxy 1 aminobenzene 1-phenyl-3-methylpyrazolone (dyestuff:chromium=2:l) and 14.0 parts of the chromium-containing monoazo dyestuff 2 hydroxy- 5 sulphomethylamido 1 aminobenzene l-carboethoxyamino 7 hydroxnaphthalene (dyestuif chromium=2: l

are incorporated in lieu of Eriochrome Black A into a pad liquor which is otherwise prepared as described in Example 19, but with Composition (c) of Example 22 as auxiliary.

Nylon fabric is impregnated with this liquor wrung out' to a liquid content of steamed for 8 minutes at a temperature of 130 and then rinsed first with hot and then with cold water.

A very well penetrated and very level olive dyeing is obtained which is free from sandwich effect and has all the other advantageous properties described hereinbefore.

Example 28 Nylon canvas is impregnated at 40 with an impregnation liquor produced according to Example 22, but with the dyestuff employed in Example 8 and using composition (a) of Example 22 as auxiliary. The goods are then wrung out to a liquid content of 50% and passed through a 98 warm aqueous bath which contains 4 ml. per liter of formic acid at such a rate that the material remains in this bath for 4 minutes. Only an inconsiderable bleeding of the dyestuff into the acid bath occurs. The nylon canvas so dyed is then rinsed first with warm and then with cold water.

The nylon canvas so obtained is well penetrated and evenly dyed olive green.

When using in lieu of the dyestufi' of Example 8, 40 parts of the dyestufi of Example 24, but following otherwise the procedure given above, nylon canvas of similar good quality and orange shade is obtained.

Example 29 Canvas made of poly e aminocaprolactam (Perlon) is impregnated at 40 with an impregnation liquor produced according to Example 23 but using the composition (a) of Example 22 as dyeing auxiliary. The goods are then wrung out to a liquid content of 50% and dried under thermo-fixing conditions for 45 seconds at The Perlon canvas so impregnated is then passed through a 98 warm aqueous bath which contains 4 ml./ liter of 85% formic acid and is treated for 4 minutes at the boil in this bath. It is then rinsed with warm and then cold water.

The Perlon canvas so treated is well penetrated and a level yellow dyeing is obtained.

Example 30 2.5 parts of the chromium-containing monoazo dyestufr 2 carboxyl 1 aminobenzene l-phenyl-3-methylpyrazolone (dyestuff:chrornium=2: l) and 0.5 part of the chromium-containing monoazo dyestuff :2 hydroxy-S-nitro-l-aminobenzene 1 phenyl 3 methyl-pyrazolone (dyestulfzchromium 2: 1) are incorporated in lieu of Eriochrome Black A into a pad liquor which is otherwise as described in Example 19.

Wool slubbing is impregnated at 40 with this liquor, wrung out of a liquid content of 103% of the dry weight and then steamed for 8 /2 minutes at 104 with saturated steam under slight excess pressure. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and l ml./liter of concentrated ammonia solution, then rinsed with water, then washed with an aqueous solution containing 2 ml./liter of 85% formic acid and, if desired, again rinsed with water.

The orange-red slubbing so dyed is well penetrated and the dyeing is very level. The feel of the goods is very pleasant and voluminous and they can be well combed and spun. Even after the impregnation liquor has been left standing for several weeks, level and well-penetrated slubbings are obtained therewith.

Example 31 40 parts of chromium-containing monoazo dyestuft: 2- hydroxy 5 sulphomethylamido 1 aminobenzene lcarboethoxyamino 7 hydroxynaphthalene (dyestutf: chromium=2:1) are stirred in a solution produced according to Example 1, paragraph 1, but containing 500 parts of sodium alginate solution instead of 300 parts.

Woollen slubbing is printed in the manner usual for vigoureux printing with this liquor with a liquor takeup of 85%. The printed goods are after-treated by steaming and rinsing as described in Example 10. Grey colored slubbing is obtained which is distinguished by a full, voluminous feel. The goods can be well combed and spun.

Example 32 13 parts of the chromium-containing monoazo dyestuff: 2 hydroxy methylsulfonyl 1 aminobenzene 1- acetylamino-7-hydroxynaphthalene are pasted with 60 parts of cold Water and then completely dissolved in 890 parts of hot water with heating to 80 (dyestulfzchromium=2:1). To the hot solution there is added while stirring a mixture of parts of locust bean flour and 3 parts of ethanol, and after cooling to 50, parts of a mixture prepared from 10 parts of coconut oil fatty acid N-methyl-N-(e-hydroxyethyl)-amide, 10 parts of sodium p-dodecyl-benzene-sulfonate and 2 parts of isopropanol. To the solution thus obtained there are added 10 parts of 80%acetic acid and 10 parts of water. The temperature of the solution should be about 50.

Wool slubbing is impregnated with this liquor at 50, the goods are squeezed out to leave a liquid content of about 105% calculated on their dry weight, and then steamed at 100-102 with saturated steam under slight excess pressure for 15 minutes. The fabric is then rinsed first with 40 warm water then with an aqueous solution of nonylphenol heptaglycol ether at 40, and finally rinsed with cold water and dried.

A very level grey wool slubbing of good penetration is obtained. It shows no sandwich effect.

If the steaming time in the above example is increased to 30 or 60 minutes, then dyeings of increasingly greater color strength but otherwise of the same value are obtained.

Dyeings of similar quality are also obtained when using in lieu of the 30 g. of dye assistant mixture mentioned above, one of the mixtures (a) to (t) of Example 22.

Example 33 16 parts of the dyestufi sulfanilic acid- 1-hydroxy- [(3' trichloropyrimidylamino) benzoylamino]-naphthalene-3,6-disulfonic acid are stirred into a paste with 40 parts of water and then dissolved by the addition of 890 parts of hot water with heating. 10 parts of carob bean flour which has been previously made into a paste with a small amount of ethanol to improve its solubility, are added while stirring. After the thickener has dissolved, the solution is cooled to 50 and then 30 parts of a dyestufi carrier mixture consisting of 15 parts of pelargonic acid- N,N-fl-hydroxyethylamide, 15 parts of sodium 1-(l,3,3,5- tetramethyl-octyl)-benzene-4-sulfonate and 2 parts of isopropanol as well as 10 parts of 85 %-formic acid and 30 parts of water are added thereto.

Wool slubbing is impregnated with this padding liquor at 50 and then squeezed out on a padding mangle to a squeezing efiect of about 100% increase in weight. The slubbing is subsequently steamed for 15 minutes in saturated steam at 100-102. After the steaming it is rinsed with warm Water of about 40 and then washed at 40 with an aqueous solution containing 1 g./liter of nonylphenolpolyglycol ether, then rinsed and dried. A red dyed slubbing without sandwich eifect is obtained.

If 5 parts of sodium copperphthalocyanine-disulfonate are used instead of 16 parts of the above mentioned azo dyestufi and otherwise the procedure given in the example is followed, then a turquoise-blue dyed slubbing of similar good quality is obtained.

If one of the mixtures (a) to (j) of Example 22 is used instead of the dyestufi carrier mixture given in the above example and otherwise the procedure given in the example is followed, then a red or turquoise-blue dyed slubbing without sandwich effect is obtained.

Example 34 80 parts of Eriochrome Black T (Mordant Black 11) and 5 parts by volume of 25% aqueous ammonia are dissolved in hot water and this solution is treated with 100 parts by volume of a 2.5% glactomannan solution and parts of a mixture of:

A mixture consisting of: 20 parts of sodium fluoride and 50 parts by volume of aqueous 20% chromium acetate solution,

which mixture has been previously brought to the boil, is added to the solution and the whole is then made up to 900 parts by volume with Warm water. 20 parts by volume 15 of aqueous 85% formic acid are added to the solution. The solution is then brought up to 1000 parts by volume by adding water. The temperature of the finished solution should be about 50.

Wool slubbing is impregnated at 50 with this dyebath, squeezed out to a liquor content of about 100% and steamed with saturated steam at 98 for 30 minutes.

Hereafter the slubbing is rinsed out at 40 in a first bath in a back-washing machine and treated for 15 to 30 seconds at a temperature of 70 in a second back-washing bath with a solution of:

10 g./ liter of sodiumbichromate and 8 ml./ liter of 85% formic acid.

The slubbing is then rinsed out in the further back- 30 washings with water of about 40.

A levelly dyed black wool slubbing is obtained which is easily combed and spun.

Example If, instead of the 2:1 chromium complex dyestuff of Example 24, 50 parts of the dyestuff mixture consisting of the orange colored 2:1 chromium complex dyestulf of the formula Q N=N- o-orn OH HO-C IUI i -ci the red dyestufi of the formula 25 (weight ratio 22:22:6) and instead of parts by volume of 85% formic acid are used and otherwise the procedure given in Example 24 is followed, then levelly dyed brown-red wool slubbing with similar properties is obtained.

Example 36 A fabric consisting of 45 parts of wool and 55 parts of polyethylene glycol terephthalate fibers is impregnated and steamed analogously to Example 24. The woolen portion of the fabric is dyed orange, while the polyester portion remains practically undyed.

Example 37 A mixed fabric of wool .and cellulose triacetate is impregnated and steamed analogously to Example 24. The woolen portion of the fabric is dyed orange, while the triacetate portion remains practically undyed.

Example 38 11 parts of the dyestutt of the formula .are dispersed in an 80 warm mixture of 200 parts of a 2.5% aqueous sodium alginate solution and 35 parts of a dyestutf carrier mixture consisting of: 20 parts of coconut fatty acid-N,N-di-,8-hydroxy-ethylamide, 15 parts of sodium p-decylphenolsulfonate and 2 parts of isopropanol. The solution obtained is made up with warm water to about 1000 parts, whereby the pH should be about 7.

Orlon-type polyacrylonitrile slubbing (containing per 100 grams of fibers 46 millimols of sulfo groups and 17 millimols of carboxyl groups) is impregnated at with this solution, squeezed out to about 100% (calculated on the dry weight) and steamed at 98 for 30 minutes with saturated steam. It is then washed out with an aqueous solution containing 1 g./liter of nonylphenolpolyglycol ether and rinsed with cold and warm water. A yellow dyed slubbing is obtained.

If, instead of the 10 parts of the given dyestuff, the same amount of 1 amino 2 methoxy-4-hydroxy-anthraquinone dyestulf is used and otherwise the procedure given in the example is followed, then red dyed orlon slubbing is obtained.

Instead of the above-mentioned orlon-type fibers, Acrilan-type acrylic fibers which are copolymers from 85% acrylonitrile and 15% vinyl acetate, can be dyed successfully with the same padding liquors and in the same manner as described in Example 38.

Example 39 Polyethyleneglycol terephthalate slubbing is impregnated at 30 with a padding liquor prepared according to Example 29 and squeezed out to a liquor content of 80%.

The slubbing is steamed at 98 for 30 minutes with saturated steam, washed subsequently with an aqueous solution containing 1 g./ liter of nonylphenol-polyglycol ether and rinsed out with warm and cold water. A levelly dyed yellow or red polyester slubbing is obtained.

If 5 parts of o-phenylphenol is added to the above padding liquor and the same procedure as given in the example is followed, then a yellow or red dyed slubbing of stronger color is obtained.

Example 40 20 parts of the dyestutf of the formula C N= 3m 9 $113 G1 I i are dissolved in a 60 warm mixture of 200 parts by volume of a 2.5% aqueous solution of Meyprogum KN and 30 parts of a dyestuff carrier consisting of:

9 parts of sodium 4-(l-methyl-undecyl) benzene-l-sulfonate,

9 parts of coconut fatty acid-N,N-bis-(,B-hydroxyethyl) amide and 250 parts by volume of water.

The solution obtained is diluted with warm water to about 900 parts by volume and the pH value of the solution is adjusted to 4 with acetic acid.

Orlon-type slubbing of the same kind as used in Example 38 is impregnated at 30 with this solution, squeezed out to about 130% (calculated on the dry weight) and steamed at 98 for 30 minutes with saturated steam. It is then washed with a solution containing 1 g./liter of nonylphenol-polyglycol ether and rinsed with warm and cold water. A yellow dyed acrylic slubbing is obtained.

If, instead of the dyestufi given above, the dyestulf Maxilon Red BL (Cl. Basic Red 22) is used and the procedure given in the example is followed, then red dyed acrylic slubbing of similar good quality is obtained.

Instead of the above orlon-type fibers, Acrilan type acrylic fibers as used in Example 38 can be dyed with the same padding liquors and in the same manner as described in Example 40, supra, and similar satisfactory results are obtained.

Example 41 360 parts of the dyestuff l-amino-6-nitro-2-hydroxynaphthalene-4-sulfonic acid Z-hydroxynaphthalene in the form of a press cake are added, while stirring, in portions to a boiler fitted with a turbo mixer already containing 360 parts of water, and stirred for one hour. In a second mixing vessel 120 parts of a dyestuif carrier mixture consisting of 60 parts of coconut fatty acid-N,N-di-(B-hydroxy-alkylamide), 60 parts of sodium 4-(l-methyl-undecyl)-benzene-sulfonate and 10 parts of 80% acetic acid are mixed. This homogeneous mixture is poured slowly, While stirring, into the dyestuff suspension and the whole is subsequently stirred for 15 minutes more, whereby a homogeneous, brown, ready-for-use dye composition is obtained.

A pad liquor is prepared from this composition by mixing 300 parts of the same with 350 parts of warm water of 60 and 100 parts of an aqueous 2.5% solution of carob bean flour thickener. 40 parts of chromium trifluoride and 20 parts of formic acid are added to the resulting solution and the dyebath is made up to 1000 parts by volume with warm water. Wool slubbing is then impregnated with this dyebath as described in Example 22.

A level-dyed black-colored wool slubbing is obtained that is easily combed and spun. The dyeing has good wash and light fastness and is free from sandwich efiect.

By following the procedure outlined in the first paragraph of Example 41, supra, and using press cakes of the other dyestuffs used in the preceeding examples, other well storable ready-for-use compositions are obtained, from which pad liquors can be easily prepared by the procedure described in the second paragraph of Example 41.

We claim:

1. In a process for the dyeing of polyamide fibers 'by impregnating them with a thicker-than-water aqueous solu- 27 tion of an acid wool dyestuff at a temperature below the drawing temperature for the dyestuff and then heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the impregnation of the fibers therewith,

( 1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of ,B-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of uand 8-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

2. In a process for the dyeing of polyamide fibers by impregnating them by a method of printing with a thicker-than-water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestuff and then heating the printed goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the printing of the fibers therewith,

(l) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of ocand fl-tetrahydronaphthalene sulfonic acids, a mixture of ,8-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and a mixture of cand ,B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and a mixture of afl-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

3. In a process for the dyeing of polyamide fibers by impregnating them by a method of coating with a thickerthan-water aqueous solution of an acid wool dyestuif at a temperature below the drawing temperature for the dyestuif and then heating the coated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the coating of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of aand [i-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral alkaline value, the simultaneous presence of auxiliaries (l) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

4. In a process for the dyeing of polyamide fibers by impregnating them by a method of spraying with a thicker-than-Water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestutf and then heating the spray-impregnated goods in a humid medium the improvement which comprises:

(a) adding to the said aqueous solution, prior to the' impregnation of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of 6-tetrahydronaphthalene sulfonic acid, a mixture of tX- and fi-tetrahydronaphthalene sulfonic acids, a mixture of j8-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

5. In a process for the dyeing of polyamide fibers by impregnating them by a method of pad dyeing with a thicker-than-Water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestutf and then heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the foulard-impregnation of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkalinevalue, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

6. In a process for the dyeing of polyamide fibers by impregnating them by a method of printing with a thicker-than-water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestuft" and then steaming the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution prior to the printing of the fibers therewith,

( 1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of uand fl-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultanneous presence of auxiliaries 1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

7. In a process for the dyeing of polyamide fibers by impregnating them by a method of coating with a thickerthan-water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestuff and then steaming the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the coating of the fibers therewith,

(l) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of ozand fl-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of onand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries 1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

8. In a process for the dyeing of polyamide fibers by impregnating them by a method of spraying with a thickerthan-water aqueous solution of an acid wool dyestuif at a temperature below the drawing temperature for the dyestuff and then steaming the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the spray-impregnation of the fibers therewith,

( 1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms With from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand fl-tetrahydronaphthalene sulfonic acid, a mixture of fl-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

9. In a process for the dyeing of polyamide fibers by impregnating them by a method of pad-dyeing with a thicker-than-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestuft and then steaming the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the foularding of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand ,B-tetrahydronapthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

10. In a process for the dyeing of polyamide fibers by impregnating them by a method of printing with a thickerthan-water aqueous solution of an acid wool dyestulf at a temperature below the drawing temperature for the dyestuff and then passing the impregnated goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the printing of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of ozand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

11. In a process for the dyeing of polyamide fibers by impregnating them by a method of coating with a thicker-than-water aqueous solution of an acid wool dyestuflf at a temperature below the drawing temperature for the dyestutf and then passing the impregnated goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the coating of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from '4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of aand ,B-tetrahydronaphthalene sulfonic 33 acids, a mixture of 6tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of 04- and fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

12. In a process for the dyeing of polyamide fibers by impregnating them by a method of spraying with a thicker-than-water aqueous solution of an acid Wool dyestufi at a temperature below the drawing temperature for the dyestufi and then passing the impregnated goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the spray-impregnation of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of a-and fl-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries 1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

13. In a process for the dyeing of polyamide fibers by impregnating them by a method of pad-dyeing with a thicker-than-water aqueous solution of an acid Wool dyestufr' at a temperature below the drawing temperature for the dyestufi and then passing the impregnated goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the foularding of the fibers therewith,

( 1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of uand fl-tetrahydronaphthalene sulfonic acids, a mixture of fl-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand s-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxaliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

14. In a process for the dyeing of polyamide fibers by impregnating them by a method of printing with a thicker-than-water aqueous solution of an acid wool dyestufl at a temperature below the drawing temperature for the dyestuif and subsequently steaming the impregnated goods in a humid medium and then passing the steamed goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the printing of the fibers therewith 1) as color transfer agent, a Water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of aand fl-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of 2- and fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (l) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

15. In a process for the dyeing of polyamide fibers by impregnating them by a method of coating with a thicker-than-water aqueous solution of an acid wool dyestufl? at a temperature below the drawing temperature for the dyestuif and subsequently steaming the impregnated goods in a humid medium and then passing the steamed goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the coating of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand fi-tetrahydronaphthalene sulfonic acids, a mixture of p-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries 1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

16. In a process for the dyeing of polyamide fibers by impregnating them by a method of spraying with a thicker-than-water aqueous solution of an acid wool dyestuif at a temperature below the drawing temperature for the dyestuti and subsequently steaming the impregnated goods in a humid medium and then passing the steamed good through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the spray-impregnation of the fibers therewith,

(l) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand fi-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of ozand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

17. In a process for the dyeing of polyamide fibers by impregnating them by a method of foularding with a thicker-than-water aqueous solution of an acid wool dyestuif at a temperature below the drawing temperature for the dyestuff and subsequently steaming the impregnated goods in a humid medium and then passing the steamed goods through a hot acid shock bath, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the foularding of the fibers therewith,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of 11- and ,B-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (l) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

18. In a process for the dyeing of polyamide fibers by applying to them a thicker-than-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestufi and heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fi-tetrahydronaphthalene sulfonic acid, a mixture of aand fl-tetrahydronaphthalene sulfonic acids, a mixture of ,B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (l) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries,

(c) applying said liquor to said fibers, and

(d) subsequently heating the impregnated fibers in said humid medium directly without intermediate drying.

19. In a process for the dyeing of polyamide fibers by impregnating them by a method of printing with a thickerthan-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestulf and heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution,

(1) as color transfer agent, a Water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of uand B-tetrahydronaphthalene sulfonic acids, a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid, and

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries,

(c) printing said fibers with the said liquor, and

(d) subsequently heating the printed goods in said humid medium directly without intermediate drying.

20. In a process for the dyeing of polyamide fibers by impregnating them by a method of coating with a thickerthan-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestuff and heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution (1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of fl-tetrahydronaphthalene sulfonic acid, a mixture of aand B-tetrahydronaphthalene sulfonic acids, a mixture of fi-tetrahydronaphthalene su1 fonic acid and thioglycolic acid, and a mixture of aand B-tetrahydronaphthalene sulfonic acids and thioglycolic acid,

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries,

(c) coating said fibers with the resulting liquor, and

(d) subsequently heating the coated goods in said humid medium directly without intermediate drying.

21. In a process for the dyeing of polyamide fibers by impregnating them by a method of spraying with a thicker-than-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestufi and heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of uand B-tetrahydronaphthalene sulfonic acids, a mixture of [i-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand fi-tetrahydronaphthalene sulfonic acids and thioglycolic acid,

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (l) and (2) preventing separation of said impregnation liquor into two phases,

35 one of which is poor and the other rich in the said auxiliaries,

(c) spray-impregnating said fibers with the resulting liquor, and

(d) subsequently heating the spray-impregnated goods in said humid medium directly Without intermediate drying.

22. In a process for the dyeing of polyamide fibers by impregnating them by a method of pad-dyeing with a thicker-than-water aqueous solution of an acid wool dyestufi at a temperature below the drawing temperature for the dyestufi" and heating the impregnated goods in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution,

(1) as color transfer agent, a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of aand fi-tetrahydronaphthalene sulfonic acids, a mixture of ,B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand ,B-tetrahydronaphthalene sulfonic acids and thioglycolic acid,

(b) adjusting the pH of the resultant impregnation liquor to a neutral to alkaline value, the simultaneous presence of auxiliaries (1) and (2) preventing separation of said impregnation liquor into two phases, one of Which is poor and the other rich in the said auxiliaries,

(c) foularding said fibers with the resulting liquor, and

(d) subsequently heating the foularded goods in said humid medium directly without intermediate drying.

23. In a process for the dyeing of polyamide fibers by impregnating them with a thicker-than-water aqueous solution of an acid wool dyestuff at a temperature below the drawing temperature for the dyestutf and then heating the fibers in a humid medium, the improvement which comprises:

(a) adding to the said aqueous solution, prior to the impregnation of the fibers therewith,

(1) as color transfer agent, a water-soluble reaction product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from among dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(2) as anionic steam-blowing control agent, a

substance selected from among:

(a) a sulfonated alkyl-benzene wherein the alkyl moiety has from 8 to 20 carbon atoms,

() sulfonated fi-tetrahydronaphthalene,

(fi') a mixture of sulfonated a and B-tetrahydronaphthalene,

(5) a mixture of sulfonated B-tetrahydronaphthalene and thioglycolic acid,

([3') a mixture of sulfonated uand ,B-tetrahydronaphthalene and thioglycolic acid,

(7) condensation products of formaldehyde or, glyoxal or acetaldehyde with per mole thereof, about 1.2 to 2 moles of at least one of the following compounds:

(5) a mixed disulfonated diaryl-alkane which is a condensation product of (i) naphthalene-sulfonic acid, (ii) a member selected from among benzene-sulfonic acid and ptoluene-sulfonic acid, and (iii) a member selected from among formaldehyde and a lower alkylene-dialdehyde of from 2 to 8 carton atoms; and

(b) adjusting the pH of the resultant impregnation liquor to a value in the range of from 2 to 9, the simultaneous presence of auxiliaries (1) and (2) suppressing the formation of sandwich effects in the dyed fibers.

24. The improvement as defined in claim 23, further comprising:

(c) applying the resulting liquor to said fibers, and

(d) subsequently heating the fibers in said humid medium directly without intermediate drying.

25. The improvement defined in claim 24, wherein said liquor is applied to said fibers by printing.

26. The improvement defined in claim 24, wherein said liquor is applied to said fibers by padding and subsequent mechanical removal of excess liquor from the fibers.

27. The improvement defined in claim 24, wherein said liquor is applied to said fibers by coating.

28. The improvement defined in claim 24, wherein said liquor is applied to said fibers by spraying the latter therewith.

29. The improvement defined in claim 26, wherein the pH of the liquid is adjusted to a neutral to alkaline value within the range given, and which improvement further comprises:

(e) passing the fibers obtained by step ((1) through an acid shock bath.

30. An impregnation liquor for the dyeing of polyamide fibers, consisting essentially of:

(1) a thicker-than-water aqueous solution of an acid wool dyestuif,

(2) as color transfer agent a water-soluble condensation product of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(3) a member selected from the group consisting of B-tetrahydronaphthalene sulfonic acid, a mixture of S-tetrahydronaphthalene sulfonic acid and thioglycolic acid, and a mixture of aand [3- tetrahydronaphthalene sulfonic acids and thioglycolic acid,

the ratio of said color transfer agent to said member defined under (3) ranging from about 2.5:1 to 4:1, the simultaneous presence of auxiliaries (2) and (3) preventing separation of said impregnation liquor into two phases, one of which is poor and the other rich in the said auxiliaries.

31. An impregnation liquor as defined in claim 30, wherein the effective amount of said color transfer agent is between 10 to 60 grams per liter.

32. An impregnation liquor as defined in claim 30, wherein the member defined under (3) is present in an amount of 2 to 20 grams per liter.

33. An impregnation liquor as defined in claim 30, wherein the member defined under (3) is B-tetrahydronaphthalene sulfonic acid.

34. An impregnation liquor as defined in claim 30, wherein the member defined under (3) is a mixture of B-tetrahydronaphthalene sulfonic acid and thioglycolic acid, the latter being present in an amount from 0.1 to 3 grams per liter of said liquor.

35. An impregnation liquor as defined in claim 30, wherein the member defined under (3) is a mixture of ocand ,B-tetrahydronaphthalene sulfonic acids and thioglycolic acid, the latter being present in an amount from 0.1 to 3 grams per liter of said liquor.

36. An impregnation liquor as defined in claim 30, wherein the color transfer agent is a water-soluble condensation product of one equivalent of coconut fatty acid with two equivalents of diethanolamine.

37. An impregnation liquor for the dyeing of polyamide fibers, consisting essentially of:

( 1) a thicker-than-water aqueous solution of an acid wool dyestuff,

(2) as color transfer agent a water-soluble condensation production of one equivalent of fatty acid having 8 to 14 carbon atoms with from one to three equivalents of a member selected from the group consisting of dialkanolamine with from 4 to 6 carbon atoms and trialkanolamine with from 6 to 9 carbon atoms, and

(3) as anionic steam-blowing control agent, a substance selected from among:

(a) a sulfonated alkyl-benzene wherein the alkyl moiety has from 8 to 20 carbon atoms,

(,8) sulfonated B-tetrahydronaphthalene,

() a mixture of sulfonated aand fl-tetrahydronaphthalene,

(5") a mixture of sulfonated fi-tetrahydronaphthalene and thioglycolic acid,

( 8") a mixture of sulfonated uand /8-tetrahydro naphthalene and thioglycolic acid,

(7) condensation products of formaldehyde, or glyoxal, or acetaldehyde with, per mole thereof, about 1.2 to 2 moles of at least one of the following compounds:

(i) benzene-sulfonic acid,

(ii) naphthalene-sulfonic acid,

(iii) tetrahydronaphthalene-sulfonic acid,

(iv) a methyl-substituted compound of (i) to (iii) inclusive, in free acid form or in the form of water-soluble salts thereof; the ratio of said color transfer agent to said member defined under (3) ranging from about 5:1 to 1:3.

38. An impregnation liquor as defined in claim 37, wherein the effective amount of said color transfer agent is between 10 to 60 grams per liter.

39. An impregnation liquor as defined in claim 37, wherein the agent defined under (3) is present in an amount of 2 to grams per liter.

40. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is B-tetrahydronaphthalene sulfonic acid.

41. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is a mixture of fl-tetrahydronaphthalene sulfonic acid and thioglycolic acid, the latter being present in an amount from 0.1 to 3 grams per liter of said liquor.

42. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is a mixture of uand fi-tetrahydronaphthalene sulfonic acids and thiogylcolic acid, the latter being present in an amount from 0.1 to 3 grams per liter of said liqour.

43. An impregnation liquor as defined in claim 37, wherein the color transfer agent is a water-soluble condensation product of one equivalent of coconut fatty acid with two equivalents of diethanolamine.

44. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is a sulfonated alkyl-benzene wherein the alkyl moiety has from 8 to 20 carbon atoms.

45. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is a mono-sulfanated-dodecylbenzene.

46. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is monosulfonated p-( 1,3 ,3 ,5 -tetramethyl-octyl) -benzene.

47. An impregnation liquor as defined in claim 37, wherein the member defined under (3) is disulfonated dinaphthyl-alkane, wherein the alkane moiety has from 1 to 2 carbon atoms, and the two naphthyl radicals are each linked to a different carbon atom thereof.

48. An impregnation liquor a-s defined in claim 37, wherein the member defined under (3) is disulfonated naphthyl-methane.

49. An impregnation liquor as defined in claim 37, wherein the ratio of said color transfer agent to said member defined under (3) is about 3:1.

References Cited UNITED STATES PATENTS 1,926,556 9/1933 Nuesslein 8-89 X 2,552,404 5/1951 Casty 854 X 2,828,180 3/1958 Sertorio 893 X NORMAN G. TORCHIN, Primary Examiner T. I. HERBERT, JR., Assistant Examiner US. Cl. X.R. 8-55, 85, 89 

